Polymerization catalyst promoter

Abstract

Compounds of the formula: <IMAGE> wherein n is 1, 2, 3, or 4; X1 and X2 are each, independently, chlorine or bromine; A is O or S; R1 is hydrogen or C1-C16 alkyl; R2 is C1-C16 alkyl, C6-C16 aryl, C1-C4 alkylidene, or CH2OR5; R3 is hydrogen, chlorine, bromine, or OR6; R4 is C1-C16 alkyl, C7-C16 aralkyl, C2-C16 alkenyl, or C6-C18 aryl; R5 is hydrogen, C1-C16 alkyl, C7-C16 aralkyl, C2-C16 alkenyl, or C6-C18 aryl; and R6 is hydrogen or C1-C16 alkyl. These compounds by themselves and in combination with certain halo-but-2-enoic acids and esters are useful as catalyst promoters in ethylene polymerization processes.

What is claimed is: 
     
       1. A compound of the formula: ##STR13## wherein n is 1, 2, 3, or 4; X 1  and X 2  are each, independently, chlorine or bromine;   A is O or S;   R 1  is hydrogen or C 1  -C 16  alkyl;   R 2  is C 1  -C 16  alkyl, C 6  -C 16  aryl, C 1  -C 4  alkylidene, or CH 2  OR 5  ;   R 3  is hydrogen, chlorine, bromine, or OR 6  ;   R 4  is C 4  -C 16  alkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl;   R 5  is hydrogen, C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl; and   R 6  is hydrogen or C 1  -C 16  alkyl, wherein R 3  is absent when R 2  is C 1  -C 4  alkylidene.   
     
     
       2. A compound as recited in claim 1 wherein n is 1. 
     
     
       3. A compound as recited in claim 2 wherein A is O. 
     
     
       4. A compound as recited in claim 3 wherein X 1  and X 2  are each chlorine. 
     
     
       5. A compound as recited in claim 4 wherein R 1  is hydrogen or C 1  -C 6  alkyl;   R 2  is C 1  -C 6  alkyl, C 1  -C 4  alkylidene, or CH 2  OR 5  ;   R 3  is hydrogen, chlorine, bromine, or OR 6  ;   R 4  is C 4  -C 6  alkyl, C 2  -C 6  alkenyl, or C 6  -C 12  aryl;   R 5  is hydrogen, C 1  -C 6  alkyl, C 2  -C 6  alkenyl, phenyl or naphthyl; and   R 6  is hydrogen or C 1  -C 6  alkyl, wherein R 3  is absent when R 2  is C 1  -C 4  alkylidene.   
     
     
       6. A compound as recited in claim 5 wherein R 1  is hydrogen or C 1  -C 4  alkyl;   R 2  is C 1  -C 4  alkyl, C 1  -C 2  alkylidene, or CH 2  OH;   R 3  is hydrogen or chlorine; and   R 4  is C 4  alkyl, C 2  -C 4  alkenyl, phenyl or naphthyl, wherein R 3  is absent when R 2  is C 1  -C 2  alkylidene.   
     
     
       7. A compound as recited in claim 6 wherein R 1  is hydrogen or methyl;   R 2  is methyl, methylene, or CH 2  OH;   R 3  is hydrogen or chlorine;   R 4  is C 4  alkyl, wherein R 3  is absent when R 2  is methylene.   
     
     
       8. A compound as recited in claim 7 having the formula ##STR14## 
     
     
       9. A composition useful in the production of ethylene copolymers comprising two or more compounds as recited in claim 1. 
     
     
       10. A composition as recited in claim 9 comprising two or more compounds as recited in claim 8. 
     
     
       11. A composition useful in the production of ethylene copolymers comprising: a) 10 to 95 weight percent of one or more compounds of the formula: ##STR15## wherein n is 1; X 1  and X 2  are each, independently, chlorine or bromine,   A is O or S;   R 1  is hydrogen or C 1  -C 16  alkyl;   R 2  is C 1  -C 16  alkyl, C 6  -C 16  aryl, C 1  -C 4  alkylidene, or CH 2  OR 5  ;   R 3  is hydrogen, chlorine, bromine, or OR 6  ;   R 4  is C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl;   R 5  is hydrogen, C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl; and   R 6  is hydrogen or C 1  -C 16  alkyl, wherein R 3  is absent when R 2  is C 1  -C 4  alkylidene; and     b) about 5 to 90 weight percent of one or more compounds selected from the compounds of the formula: ##STR16## wherein: X, X 1 , X 2  and X 3  are each, independently, chlorine or bromine; A is oxygen or sulfur;   R 5  is hydrogen or C 1  -C 16  alkyl, preferably, hydrogen or C 1  -C 6  alkyl;   R 6  is C 1  -C 16  alkyl, preferably, C 1  -C 6  alkyl;   R 7  is hydrogen, C 1  -C 16  alkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl, preferably, hydrogen or C 2  -C 12  alkyl; and   R 8  is hydrogen, C 1  -C 16  alkyl or C 1  -C 4  alkylidene, preferably, hydrogen or C 1  -C 6  alkyl, wherein X 3  is absent when R 8  is C 1  -C 4  alkylidene.     
     
     
       12. A composition as recited in claim 11 wherein R 5  is hydrogen or C 1  -C 6  alkyl;   R 6  is C 1  -C 6  alkyl;   R 7  is hydrogen or C 2  -C 12  alkyl; and   R 8  is hydrogen or C 1  -C 6  alkyl.   
     
     
       13. A composition useful in the production of ethylene copolymers comprising about 30 to 90 weight percent of one or more compounds as recited in claim 8 and about 10 to 70 weight percent of one or more compounds selected from the group consisting of compounds of the formula ##STR17## 
     
     
       14. A process for the preparation of alpha-olefin polymers comprising reacting ethylene, at least one monomer having the structural formula CH 2  ═CHQ where Q is an alkyl having 1 to 8 carbon atoms and, optionally, a non-conjugated diene, in the presence of a catalytically effective amount of a catalyst composition comprising: (a) a vanadium-containing compound;   (b) an organoaluminum compound; and   (c) one or more compounds of the formula: ##STR18## wherein n is 1, 2, 3, or 4;   X 1  and X 2  are each, independently, chlorine or bromine;   A is O or S;   R 1  is hydrogen or C 1  -C 16  alkyl;   R 2  is C 1  -C 16  alkyl, C 6  -C 16  aryl, C 1  -C 4  alkylidene, or CH 2  OR 5  ;   R 3  is hydrogen, chlorine, bromine, or OR 6  ;   R 4  is C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl;   R 5  is hydrogen, C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl; and   R 6  is hydrogen or C 1  -C 16  alkyl, wherein R 3  is absent when R 2  is C 1  -C 4  alkylidene.   
     
     
       15. A process as recited in claim 14 wherein n is 1. 
     
     
       16. A process for the preparation of alpha-olefin polymers comprising reacting ethylene, at least one monomer having the structural formula CH 2  ═CHQ where Q is an alkyl having 1 to 8 carbon atoms and, optionally, a non-conjugated diene, in the presence of a catalytically effective amount of a catalyst composition comprising: (a) a vanadium-containing compound;   (b) an organoaluminum compound; and   (c) one or more compounds as recited in claim 8.   
     
     
       17. A process for the preparation of alpha-olefin polymers comprising reacting ethylene, at least one monomer having the structural formula CH 2  ═CHQ where Q is an alkyl having 1 to 8 carbon atoms and, optionally, a non-conjugated diene, in the presence of a catalytically effective amount of a catalyst composition comprising: (a) a vanadium-containing compound;   (b) an organoaluminum compound; and   (c) a composition as recited in claim 11.   
     
     
       18. A process for the preparation of alpha-olefin polymers comprising reacting ethylene, at least one monomer having the structural formula CH 2  ═CHQ where Q is an alkyl having 1 to 8 carbon atoms and, optionally, a non-conjugated diene, in the presence of a catalytically effective amount of a catalyst composition comprising: (a) a vanadium-containing compound;   (b) an organoaluminum compound; and   (c) a composition as recited in claim 13.   
     
     
       19. A process for the preparation of EPDM comprising reacting ethylene, propylene, and a non-conjugated diene, in the presence of a catalytically effective amount of a catalyst composition comprising: (a) a vanadium-containing compound;   (b) an organoaluminum compound; and   (c) one of more compounds of the formula: ##STR19## wherein n is 1, 2, 3, or 4; X 1  and X 2  are each, independently, chlorine or bromine;   A is O or S;   R 1  is hydrogen or C 1  -C 16  alkyl;   R 2  is C 1  -C 16  alkyl, C 6  -C 16  aryl, C 1  -C 4  alkylidene, or CH 2  OR 5  ;   R 3  is hydrogen, chlorine, bromine, or OR 6  ;   R 4  is C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl;   R 5  is hydrogen, C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl; and   R 6  is hydrogen or C 1  -C 16  alkyl, wherein R 3  is absent when R 2  is C 1  -C 4  alkylidene.     
     
     
       20. EPDM produced in accordance with the process as recited in claim 19. 
     
     
       21. A process for the preparation of EPM comprising reacting ethylene and propylene, in the presence of a catalytically effective amount of a catalyst composition comprising: (a) a vanadium-containing compound;   (b) an organoaluminum compound; and   (c) one or more compounds of the formula: ##STR20## wherein n is 1, 2, 3, or 4; X 1  and X 2  are each, independently, chlorine or bromine;   A is O or S;   R 1  is hydrogen or C 1  -C 16  alkyl;   R 2  is C 1  -C 16  alkyl, C 6  -C 16  aryl, C 1  -C 4  alkylidene, or CH 2  OR 5  ;   R 3  is hydrogen, chlorine, bromine, or OR 6  ;   R 4  is C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl;   R 5  is hydrogen, C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl; and   R 6  is hydrogen or C 1  -C 16  alkyl, wherein R 3  is absent when R 2  is C 1  -C 4  alkylidene.     
     
     
       22. EPM produced in accordance with the process as recited in claim 21. 
     
     
       23. In a process for the production of a copolymer of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes, which process comprises reacting the ethylene with the comonomer in the presence of a catalyst composition comprising a vanadium-containing compound, an organoaluminum compound, and a catalyst promoter, wherein the improvement comprises a promoter comprising one or more compounds of the formula: ##STR21## wherein n is 1, 2, 3, or 4; X 1  and X 2  are each, independently, chlorine or bromine;   A is O or S;   R 1  is hydrogen or C 1  -C 16  alkyl;   R 2  is C 1  -C 16  alkyl, C 6  -C 16  aryl, C 1  -C 4  alkylidene, or CH 2  OR 5  ;   R 3  is hydrogen, chlorine, bromine, or OR 6  ;   R 4  is C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl;   R 5  is hydrogen, C 1  -C 16  alkyl, C 7  -C 16  aralkyl, C 2  -C 16  alkenyl, or C 6  -C 18  aryl; and   R 6  is hydrogen or C 1  -C 16  alkyl, wherein R 3  is absent when R 2  is C 1  -C 4  alkylidene.